Production of ethylene polymers and ethylene copolymers

ABSTRACT

WHEREIN R AND R2 REPRESENT INDEPENDENTLY MEMBERS SELECTED FROM THE GROUP CONSISITNG OF ALKYL GOUPS HAVING ONE TOO FIVE CARBON ATOMS, CYCLOHEXYL, PHENYL AND 1-NAPHTHYL; X1 AND X2 REPRESENT MEMBERS SELECTED FOM THE GROUP CONSISITNG OF ALKYLS HAVING ONE TO FIVE CARBON ATOMS, CYCLOALKYLS HAVING FOUR TO SIX CARBON ATOMS, PHENYL, P-TOYL AND HALOGENS SELECTED FROM THE GROUP CONSISTING OF CL, BR, AND I AND AT LEAST ONE OF X1 AND X2 REPRESENTS SAID HALOGEN, AND (B) AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1. TIX3P, VX3P, TIX34-Q(OR3)Q, VOX33-R(OR3)R AND VOX33 WHEREIN X3 REPRESENTS HALOGEN SELECTED FROM THE GROUP CONSISTING OF CL, BR, AND I; R3 REPRESENTS ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYS HAVING ONE TO SIX CARBON ATOMS, CYCLOHEXYL, PHENYL AND P-TOYL; P IS AN INTEGER OF 2 TO 4, Q IS AN INTEGR OF 1 TO 3; R IS AN INTEGER OF 1 TO 2; AND 2. THE SOLID COMPOUNDS OBTAINED BY THE REACTION BETWEEN ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF TIX34, VX34, TIX34-Q(OR3)Q, VOX33-RAND VOX33 AND ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF AIR4R(OR5)UX33-Y, SIR63H, (R7HSIO)G, R8R9R10SIO-(R11SIO)T-SIR10R9R8 AND A COMBINATION OF ONE MEMBER SELECTED FROM SIRR63H, (R7HSO)G AND R8R9R10SIO-(R11HSIO)T-SIR10R9R8 AND ONE MEMBER SELECTED FROM ALCL3, ALBR3AND FECL3 WHEREIN R3 AND X3 REPRESENT INDEPENDENTLY THE SAME GROUPS AS DEFINED ABOVE; R4 AND R5 REPRESENTS INDEPENDENTLY THE SAME GROUPS ABOVEDEFINED R3; R6, R7, R8, R9, R10 AND R11 REPRESENT INDEPENDENTLY THE SAME GROUPS AS ABOVE-DEFINED R1 OR R2; Q AND R REPRESENT INDEPENDENTLY THE SAME INTEGERS AS ABOVE-DEFINED; V IS AN INTEGER OF 1 TO 3, W IS 0 OR AN INTEGER OF 1 TO 2, Y IS AN TEGER OF 1 TO 3 AND V+N+Y=3; S IS AN INTEGER OF 3 TO 6+ T IS AT LEAST ONE AND THE VISOSITY OF R8R9R10SIO-(R11HSIO)TSIR10R9B8 IS AT MOST 2,000 CENTISTROKES, THE MOLE RATIO OF THE COMPOUND (A) TO THE COMPOUND (B) BEING 0.5 - 5 : 1.   R1R2HSIOALX1X2   THE POLYMERIZATION OF ETHYLENE AND THE COPOLYMERIAZTION OF ETHYLENE WTH ONE ALPHA-OLEFIN HAVING THREE TO 10 CARBON ATOMS IN THE PRESENCE OF A CATALYST PREPARED BY THE REACTION BETWEEN 8A) AT LEAST ONE COMPOUND OF THE GENERAL FORMULA;   D R A W I N G

United States Patent [191 Aishima et a1.

[451 Jan. 22, 1974 PRODUCTION OF ETHYLENE POLYMERS AND ETHYLENE COPOLYMERS [73] Assignee: Asahi Kasei Kogyo Kabushiki Kaisha, Tokyo, J a'pan [22] Filed: Nov. 17, 1971 21 Appl. No.: 199,785

Related [1.8. Application Data Continuation of Ser. No. 840,187, July 9, 1969, abandoned.

Foreign Application Priority Data July 16, 1968 Japan 43/49654 [52] US. Cl. 260/882 F, 23/110, 252/429 R, 252/429 B, 260/882 R, 260/949 B, 260/94.9 C, 260/949 E [51] Int. Cl C08f 1/44, C08f 3/06, C08f-l5/04 [58] Field of Search 260/949 B, 94.9 C, 260/949 E, 88.2 R, 88.2 F; 252/429 B [56] References Cited UNITED STATES PATENTS 3,661,878 5/1972 Aishima et a1. 260/949 C 3,202,617 8/1965 Enk et a1 260/949 E Primary ExaminerJames A. Seidleck Assistant Examiner-A. Holler Att0rney-Ralph D. Dinklage et al.

[57] ABSTRACT The polymerization of ethylene and the copolymerization of ethylene with one alpha-olefin having three to 10 carbon atoms in the presenceof a catalyst prepared by the reaction between (A) at least one compound of the general formula;

wherein R and R represent independently members selected from the group consisting of alkyl groups having one to five carbon atoms, cyclohexyl, phenyl and l-naphthyl; X- and X represent members selected from the group consisting of alkyls having one to five carbon atoms, cycloalkyls having four to six carbon atoms, phenyl, p-tolyl and halogens selected from the group consisting of Cl, Br and I and at least one of X and X represents said halogen, and (B) at least one compound selected from the group consisting of the group consisting of Cl, Br, and l; R represents one member selected from the group consisting of alkyls having one to six carbon'atoms, cyclohexyl, phenyl and p-tolyl; p is an integer of 2 to 4, q is an integer of l to 3; r is an integer of l to 2; and

2. the solid compounds obtained'by the reaction between one member selected from the group consisting of TiX VX TiX ,,(OR VOX ,and VOX and one member selected from the group consisting of AIR ,,(OR ),,,X SiR H, (R HSiO) of one member selected from SiR l-I, (RTHSiO), and R'*R"RSiO-(Rl-1Si0),-SiRR"R and one member selected from AlC1 AlBr and FeCl wherein R and X represent independently the same groups as defined above; R and R represents independently the same groups'above-defined R; R, R R R R and R" represent independently the same groups as above-defined R or R; q and r represent independently the same integers as above-defined; v is an integer of l to 3, w is 0 or an integer of l to 2, y is an integer of l to 3 and v+w+y=3; s is an integer of 3 to 6; t is at least one and the viscosity of RR"RSiO-(RHSiO),-SiRRR is at most 2,000 centistrokes, the mole ratio of the compound (A) to the compound (B) being 0.5 5 l.

CVCLOPENTANE PRODUCTION OF ETHYLENE POLYMERS AND ETHYLENE COPOLYMERS This application is a continuation of application Ser. No. 840,187, filed July 9, l969, now abandoned.

- This invention relates to the production of crystalline ethylene polymers and ethylene copolymers.

Heretofore, a variety of catalysts for polymerizing alpha-olefins have been proposed and each of the catalysts has its own characteristics.

For example, Japanese Pat. No. 282,694 describes a process for polymerizing ethylene, propylene or vinyl chloride using a catalyst prepared by treating a halide of transition metals such as TiCl .TiCl VCL, and CrCl or an alkoxide of transition metals with a siliconcontaining compound having group such as triethyl silane and methyl hydrogen silicone oil. In that process there is the formation of anomalous polymers and it is difficult to continuously operate the polymerization reaction. Further, the ethylene polymers according to that process have a low bulk density and a relatively high degree of branching and are not uniform in particle size.

It is an object of this invention to provide novel catalysts for the production of crystalline ethylene polymers and ethylene copolymers.

It is another object of this invention to provide a process for polymerizing ethylene or copolymerizing ethylene with one alpha-olefin having three to 10 carbon atoms by using said novel catalysts.

Other and additional objects of this invention will become apparent from a consideration of this entire specification including the claims hereof.

In accord with and fulfilling these objects, one aspect of this invention resides in a catalyst obtained by the reaction of (A) at least one compound containing silicon and aluminum represented by the formula;

R R HSiOAIX'X wherein R and R represent independently alkyls having one to fivecarbon atoms such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl and normal pentyl, aryls such as phenyl and l-naphthyl, and cycloalkyls such as cyclohexyl; X and X represent independently alkyls having one to five carbon atoms such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl and normal pentyl, aryls such as phenyl and p-tolyl, cycloalkyls such as cyclobutyl, cyclopentyl and cyclohexyl and halogens such as C Br, and I and at least one of X and X represents said halogen; and (B) at least one titanium or vanadium compound containing at least one halogen selected from;

- 1. TiX VX TiX (OR VOX ,(OR and VOX wherein X represents halogen such as Cl, Br, and I; R represents alkyl having one to six carbon atoms such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and normal hexyl, cycloalkyl such as cyclohexy], and aryl such as phenyl and p-tolyl; p is an integer of 2 to 4, q is an inte ger of l to 3; r is an integer of 1 to 2; and

2. the said compounds obtained by the reaction of TiXj, VX TiX (R VOX ,(OR or VOX and AlR,,(OR X SiREl-l, (R HSiO),, R RRSiO-( RHSiO),-SiRR R or a combination of one member selected from SiR H, (RHSiOL, and RR RSiO-(RHSiO),-SiR "R"R and one member selected from AlCl AlBr and FeCl;, wherein R and X represent independently the same groups as defined above; R and R represents independently the same groups above-defined R"; R, R", R R", R and R represent independently the same groups as above defined R or R q and r represent independently the same integers as above-defined; v is an integer of l to 3, w is 0 or an integer of l to 2, y is an integer of l to 3 and v+w+y=3, s is an integer of 3 to 6; t is at least one and the viscosity of R RRSiO(RHSiO),-SiRR"R is at most 2,000 centistrokes, the mole ratio of (A) the compound containing silicon and aluminum to (B) the titanium or vanadium compound containing at least one halogen being 0.5 5 l.

It has now been found that by using such catalyst in the polymerization of ethylene, the polymers having a high bulk density may be produced and a series of the manufacturing steps such as polymerization, purification, separation, drying and pelletization may all be made small size and simplified. Additionally, the handling-of such powdery polymers is easy since the particle size of polymers is relatively large and uniform and there is no danger of explosion due to fine powdery polymers and the melt-extruding step for pelletization is remarkably easy and accordingly a special device for feeding powdery polymers is not required. Further, a continuous operation of polymerization may be very easily effected since there is no formation of anomalous polymers such as the ones adhered to the wall of reactor or the bulky ones. Furthermore, only by selecting a combination of (A) the compound containing silicon and aluminum and (B) the titanium or vanadium compound containing at least one halogen even under the same polymerization conditions there may be easily produced a variety of polymers such as the ones having a high linearity for the production of containers and the ones having a comparatively high degree of branching to be used in an air molding.

Another aspect of this invention resides in the copolymerization of ethylene with one alpha-olefin having three to 10 carbons by using the catalyst abovementioned.

According to this invention, examples of suitable compounds containing silicon and aluminum include (Cl-l l-lSiOAlCl (CH HSiOAlBr (CH HSi- OAll (C H HSiOAlCl (C H HSiOAlBr (C H HSiOAlI (nC H HSiOAlCl (n-C H HSiOAlBI'z, (nC3H7)2HsiOAlI2, (i-C Hfl l-lsiOAlBr (i-C H HSiOAlI (n-C H HSiOAlCl (nC H HSiOAlBr (n-C H HSiOAlI (iC H9)2HSiOAlBr2, (iC4H9)2.

These compounds are all stable novel compounds having a low vapor pressure and accordingly the pres ent invention may be carried out safely.

These compounds are formed by the reaction:

1. between RR HSiOSiHR R and AIR X or AIR R X and 2. between (Rl-lSiO) or RRRSiO-(R' HSiO),-SiRR R and AlR x or AlR R X wherein R, R R R R R, R and X represent independently the same groups as define afore; R and R represent independently alkyls having one to five carbon atoms, cycloalkyls such as cyclobutyl, cyclopentyl and cyclohexyl and aryls such as phenyl and p-tolyl; X represents the same group as defined above.

These reactions may be effected in the presence or absence ofa solvent such as a hydrocarbon at a temperature of room temperature to 210C. in an inert atmosphere such as nitrogen.

The details of a process for preparing the compounds containing silicon and aluminum will be illustrated in the following.

According to the process (I), in a 500 ml. stainless steel vessel there are charged 26.8 g. of dimethyldihydrodisiloxane [(CH HSiOSil-l(Cl-1 and 18.4 g. of (Cl-l AlCl and the reaction vessel is closed and left to stand at 200C. for hours. After the reaction is completed, the vessel is cooled to room temperature and the content of the vessel is distilled to remove the distillate having a low boiling point and the remaining substance is distilled under reduced pressure to give 13.4 g. of the reaction product. This product has a boiling point of 57C. at 2 mm. Hg. and is identified with (CH HSiOAlCl(CH by the NMR spectrum analysis, the infra red absorption spectrum and the elementary analysis.

According to the process (2), in a 500 ml. glass reactor equipped with a stirrer there are charged 36.0 g. of (Cl-l AlCl, 23.4 g. of cyclic methylhydropolysiloxane [(CH )HSiO]., and 200 m1. of n-heptane and the reaction is carried out at 40C. for 24 hours in a nitrogen atmosphere with stirring. The reaction product is distilled under reduced pressure to give 42 g. of the main distillate. This distillate has a boiling point of 56.5 to 570C. at 2 mm. Hg. and is identified with (CH HSi- OAlCl(Cl-l by the NMR spectrum analysis.

In the same manner, (CH HSiOAlCl is obtained by the reaction between (CH )AlCl and [(CH )HSiO] This reaction quantitatively proceeds at a temperature between 40 and 50C. in accordance with the following equation,

CH1 Cl l, Minimum unison-A til-4) It is easily confirmed by the analysis of NMR spectrum of the reaction product what the structure of the reaction product is and whether the reaction have proceeded quantitatively. The NMR spectrum of thus obtained product is measured using a concentration of about 1 mole of the product per 1 l. of cyclopentane is shown in the accompanying FIGURE which exhibits the presence of bonds of two methyl groups and one hydrogen atom to silicon, the absence of bonds of methyl group to aluminum and the absence of the unreacted [(CHQHSiO], and the free (CH )AlC1 in an unreacted state. Thus obtained compound of the formula;

is soluble in hydrocarbon solvents and either the reaction solution as such may be employed as one component of the polymerization catalyst or the compound may be employed after being purified by distillation. The both exhibit the same behavior in the polymerization reaction. It is to be noticed as an interesting fact that this compound containing silicon and aluminum shown by the above-described formula does not have any aluminum-carbon bond and forms a catalyst having a high activity for polymerizing ethylene. Furthermore, the presence of the silicon-hydrogen bond shown in the above-described formula is an indispensable structural factor and the compound in which the silicon-hydrogen bond is substituted with a hydrocarbon group such as methyl represented by the formula;

does not exhibit such a remarkable activity as the ones of this invention when employed in the present invention.

Examples of suitable titanium or vanadium compounds containing at least one halogen include TiCl TiCl TiCl VCl VCl VCl TiBr TiBr TiBr VBr VBr VBr Til Til Til V1 V1 V1 TiCl- (OCH TiCl (0C H TiC1 (O n-C H TiCl (O n-C H, TiCl (O cyclo C 11 TiCl (OC H TiCl- (O p-CH C 1-1 TiBr (O CH TiBr (O C 11 TiBr- (O n-C 1-l TiI (O CH Ti1 (O C 11 Til (O n-C H TiI (O i-C l-l TiI (O n-C H TiCl (O CH TiCl (O C 11 TiCl (O nC l-1 TiC1 (O i-C l-lfl TiC1 (O n-C 1-1 TiCl (O i-C H TiCl (O CyClO C Hu)2, P-CH3CGH4)Z, CH3)2, Ti1 (O C l-1 Til (O i-C H TiCl (O CH TiCl(O C H TiCl(O n-C l-l TiCl(0 i-C H TiCl(0 n-C I-1 TiCl(O i-C 1-l TiCl(O n-C H TiCl(O C H Ti1(0 nC 1-l TiI(O i-C H,) VOCl (0 CH VOCl (O C 11 VOCl (O n-C H VOCl (O iC 1-1 VOBr (O nC 1-l VOBr (O i-C l-1,), VOBr (O n-C H VOBr (O PC 11 VOl (OC1-l V01 z s), 2( 5 l1)a z( y e u), VOl (O n-C l-l VOC1(O CH VOCl(O C HQ VOCl(O n-C H VOCl(O i-C H,) VOBr(O CH VOBr(OC H,-,) VOBr(O i-C H VO1(O CH VOl(O C H VOCI VOBr and V01 and the solid compounds obtained by the reaction between one member selected from TiCl TiCl (O n-C I-l VCl, and VOCl and one member selected from Al(C H 2 5)2 2( 2 5), C2H5)(C2H5)21 4 9)3, I 4H9)z ah 2 5)3 s [(CH )HSiO],,, (CI-I SiO [(CH )l-ISiO'] -Si(CI-I and a combination of one member selected from (C2H5)3SIH, and (CH SiO-[(CH )HSiO] Si(CH and one member selected from AlCl AlBr and FeC1 The reaction of these two catalyst components may be effected at a temperature of 70 to 100C. in an inert reaction medium including aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic hydrocarbons such as cyclohexane .and methyl cyclohexane. It is possible to add the two components of catalyst in the polymerization system and to react the two components of catalyst under the polymerization conditions inthe course of polymerization reaction or to react the components of catalyst prior to the polymerization reaction. The mole ratio of the titanium or vanadium compound to the compound containing silicon and aluminum is preferably in the range of 1:0.5

obtain a catalyst having a high activity.

The alpha-olefins having three to 10 carbon atoms which are copolymerizable with ethylene, include propylene, butene-l, 3-methylbutene-l, pentene-l, 4-methylpentene-1, hexene-l heptene-l octene-l nonene-l and decene-l.

According to the present invention, the ethylene copolymers contain at most 10 weight percent of the 'alpha-olefin.

In the production of the polymers and copolymers, polymerization may be conducted with or without a reaction medium, and the preferable, reaction medium is an aliphatic, alicyclic or aromatic hydrocarbon inert to each of the catalyst components, such as, for example, butane, n-hexane, isooctane, benzene, toluene, xylene, tetrahydronaphthalene,cyclohexane, methylcyclohexane and the like.

The ratio of such a'solvent to ethylene or together with the alpha-olefin may arbitrarily be determined according to the mode of polymerization. Ordinarily, however, it is preferable to employ less than 100 parts by weight of the solvent per part by weight of ethylene or together with the alpha-olefin.

The catalyst is charged in a reactor together with a reaction medium and, for example, ethylene is induced thereto at a pressure of l to 20 Kg./cm in an inert atmosphere. The polymerization is effected at a temperature of room temperature to 150C. In order to control a molecular weight of, hydrogen gas, a halogenated hydrocarbon such as carbon tetrachloride and carbon tetraiodide or an organo-metallic compounds capable of easily causing the chain transfer reaction such as diethyl zinc may be introduced or added to the reaction system. It is preferred to introduce hydrogen gas in proportion of at most 50 mole percent based upon the ethylene reactant or together with the alpha-olefin reactant.

This invention will be illustrated by the following examples which are in no way limiting upon the scope thereof. Viscosities are intrinsic viscosities measured using a concentration of 0.1 gram of thepolymer per 100 cc. of tetralin at 135C.

EXAMPLE 1 The first catalyst component of (CI-I I-ISiOAlCl was prepared as follows. In a 500 ml. glass reactor equipped with a stirrer 36.0 g.;of (CH )A1Cl 19.0 g.

of-[(.CH )1-ISiO] and 220 ml. of cyclopentane were charged and reacted at 40C. for 24 hours under a nitrogen atmosphere with stirring. The reaction product was colorless transparent liquid. The reaction proceeded quantitatively according to the equation (1). The reaction product shown in the abovadescribed equation was a nearly pure compound and the unreacted reagents were not found from'a NMR analysis of the reaction product. Accordingly, the reaction solution as such was used in the polymerization.

0.72 g. of TiCl 1.4 g. of (CH HSiOAICI and 20 ml. of n-heptane were charged in a 50 mhflask and stirred in a nitrogen atmosphere at room temperature for 30 minutes to prepare a catalyst. Thus obtained catalyst was charged in a 2.0 l. autoclave which had been vacuumed and l l. of degassed and dehydrated nheptane was added thereto. The autoclave was heated and ethylene was introduced thereto for 2 hours with stirring while maintaining the inner temperature of the autoclave at C. and the inner pressure at 5 KgJcm After the polymerization was completed, isopropyl a1- cohol was added to decompose the catalyst and the polymers were filtered off and dried. There were obtained 321 g. of white powdery polymers having an intrinsic viscosity of 5.7 and a bulk density of 0.41. The distribution of the particle size of polymers was narrow and the polymers having a particle size of 0.15 to 0.2 mm. were 68- percent by weight and the formation of ribbonor bulk-shaped polymers was not observed.

EXAMPLE 2 A compound containing silicon and aluminum represented by the formula; (CH HSiOA1(CH )Cl was prepared in the same manner as in Example 1, except that 29.8 g. of (CH AlCl were used instead of (CH )AlCl 6.0 g. of TiCl and 9.4 g. of (CH l-ISiOAl(Cl-l )Cl were reacted in 160 ml. of the paraffin hydrocarbons having a point of to C. under a nitrogen atmosphere at room temperature for 1 hour. Then the resulting reaction mixture was charged in a 15 1. glasslined autoclave with a stirrer and 8 l. of the sufficiently dehydrated paraffms. A hydrogen-ethylene mixture containing 0.30 percent of hydrogen was introduced thereto for 3.5 hours with stirring while maintaining the inner temperature of the autoclave at 30C. and the inner pressure at 5 Kg./cm After the polymerization was completed, methyl alcohol was added to decompose the catalyst and the polymers were filtered off and dried. There were obtained 3.3 Kg. of white powdery polymers having an intrinsic viscosity of 1.43, an true density of 0.956 anda bulk density of 0.40. Neither adhesion of the polymers to the autoclave nor the formation of ribbonor bulk-shaped polymers was observed. The distribution of the particle size of polymers was narrow and the polymers having a particle size of 0.15 to 0.2 mm. were 74 percent by weight; Furthermore, the melt-extrusion of thus obtained polymers by a pelletizer was operated efficiently and smoothly to give white pellets.

EXAMPLE 3 In the same manner as in Example 1 except that 1.1'

g. of TiCl, (O,,-C l-l instead of TiCl, were employed, the polymerization was carried out and 396 g. of white powdery polymers having an intrinsic viscosity of 6.4 and a bulk density of 0.41. t

EXAMPLE 4 In the same manner as in Example 1, except that instead of ethylene a hydrogen-ethylene mixture containing 0.25 percent of hydrogen was employed, the polymerization was carried out and 324 g. of white powdery polymers of uniform size having an intrinsic viscosity of 1.20, a true density of 0.963 and a bulk density of 0.39.

EXAMPLE 5 The catalyst was prepared as follows. 6.7 g. of AlCl 22 ml. of methylhydropolysiloxane having a viscosity of 100 centistrokes at 30C. which terminals had been blocked with trimethylsilyl group and 13.4 ml. of TiCl were added to 200 ml. of ligroin having a boiling point of 70C. to 80C. and the reaction was carried out at 85C. for 2 hours to give a reaction solution containing brown precipitates. These precipitates were filtered off using glass fibers, washed with 200 ml. of ligroin, transferred to an Asahina-type extractor for a continuous operation, extracted and washed with n-heptane over 72 hours. After removing off the solvent under vacuum there were obtained 10.6 g. of solid product. The analytical results of thus obtained solid substance is shown in Table 1.

Thus obtained brown solid product consists of complicated compounds or complexes containing titanium, silicon, aluminum, oxygen, chlorine, carbon and hydrogen. The compound containing silicon and aluminum represented by (CH HSiOAlCl was prepared in the same manner as in Example I.

1.2 g. of the above-mentioned solid product and 3.4 g. of (Cl-l SiOAlCl were charged in a 1.7 1. autoclave with a stirrer and the autoclave was vacuumed. 800 ml. of ligroin were inhaled in the autoclave and ethylene was introduced thereto for 2 hours with stirring while maintaining the inner temperature of the autoclave at 85C. and the inner pressure at 3 Kg./cm After the polymerization was completed, isopropyl alcohol was added to decompose the catalyst. There were obtained 270 g. of white powdery polymers having an intrinsic viscosity of 2.61, a true density of 0.951 and a bulk density of 0.41. The distribution of the particle size of polymers was very narrow and the polymers having a particle size of 0.15 to 0.2 mm. were 65 percent by weight and the formation of ribbonor bulk-shaped polymers was not observed.

EXAMPLE 6 30 g. of the compound containing silicon and aluminum represented by (CH )(C H )HSiOAl(C l-l )Cl prepared in the same manner as in Example 2 except that 38.8 g. of(C H AlCl was used, and 19 g. ofTiCl were added to 200 ml. of ligroin and the reaction was carried out at room temperature for 2 hours to obtain a reaction solution containing brown precipitates. The

reaction products were filtered off in an inert atmosphere and the solid substance was washed with 400 ml. of ligroin and after removing off the solvent under vacuum, 16 g. of solid substance was obtained.

1.0 g. of the above-mentioned solid substance and 4.0 g. of (CI-l (C H,)HSiOAl(C H )Cl were charged in a 1.7 l. autoclave with a stirrer and the autoclave was vacuumed. 800 ml. of ligroin were inhaled in the autoclave and ethylene was introduced thereto for 2 hours with stirring while maintaining the inner pressure at 3 Kg./cm and a temperature at C. After the polymerization was completed, methyl alcohol was added to decompose the catalyst and there were obtained 307 g. of white powdery polymers of uniform particle size having an intrinsic viscosity of 3.94 and a bulk density of 0.37.

EXAMPLE 7 In the same manner as in Example 1, except that 1.0 g. of beta-TiCl was used instead of TiCl, the polymerization was carried out and 321 g. of white powdery polymers of uniform particle size having an intrinsic viscosity of 2.17 and a bulk density of 0.41.

EXAMPLE 8 1n the same way as in Example 1, except that instead of TiCl.,, 0.73 g. of VCl, was used, the polymerization was carried out and 307 g. of white powdery polymers of uniform particle size having an intrinsic viscosity of 0.47 and a bulk density of 0.37.

EXAMPLE 9 In the same way as in Example 1, except that 39 g. of [(C H )HSiO] prepared in the same process as described in .1. Am. Chem. Soc., 79, 1437 (1957) were used instead of [(CH )HSiO] the polymerization was carried out and 341 g. of white powdery polymers of uniform particle size having an intrinsic viscosity of 3.9 and a bulk density of 0.39.

EXAMPLES 10 TO 18 A mixture of n-heptane and a comonomer set forth in Table II was prepared by mixing 1 l. of degassed nheptane with 10 g. of the comonomer in the following manner. Gaseous propylene, butene-l and 3- methylbutene-l from a bomb were independently condensed in an autoclave cooled with dry ice. The other comonomers were independently weighed in a pressure ampoule at room temperature. 10 g. of thus obtained comonomer and 1 l. of n-heptane were placed in an autoclave which had been vacuumed, and the autoclave was shaken to produce a mixture of n-heptane and the comonomer.

In the same manner as in Example 1, the catalyst was introduced in an autoclave and the above-mentioned mixture of n-heptane and the comonomer instead of l l. of heptane was added thereto. Then the polymerization was carried out in the same manner as in Example 1 and the formation of ribbonor bulk-shaped polymers was not observed. The results are shown in Table 11.

TABLE 11 Polymer Content of lntrin- Example Yield Comonomer Bulk sic No.

Comonomer (gram) by Density Visco- No. weight) sity 10 The content of a comonomer was calculated from the absorption at 1,378 cm of the infra red absorption spectrum.

EXAMPLES 19 to 29 The polymerization of ethylene was carried out in the same way as in Example 4 except that 4 mmoles of a variety of titanium or vanadium compounds and 8 mmoles of a variety of compounds containing silicon and aluminum set forth in Table 111 were employed. The results are shown in Table 111. All polymers thus FeCl wherein R and X represent independently the same groups above; defined above R and R represents independently the same groups abovedefined R R R R R R and R represent independently the same groups as above defined R or R q and r represent independently the same integers as above-defined; v is an integer of 1 to 3, w

is or an integer of l to 2, y is an integer of l to 3 andv-l-w+y=3;sisanintegerof3to6;ris

at least the of RR R"SiO-(R 1-1SiO),-SiRRR most 2,000 centistrokes, the mole ratio of the compound (A) to the compound (B) being 0.5 :1.

2. A process according to claim 1, wherein the comone and viscosity is at pound of the general formula;

obtained had a uniform particle size. RWHSiOAlXX TABLE III IURHSiOAlXX Polymer Titanium 0r vanadium yield Intrinsic Bulk Exampie N0. compound R R X X (gram) viscosity density 'P1Cl(OCII C1115 n-CaHr Br n-C3H1 362 1. 73 0. 41 'IlBrflOCfll C11; n-C4Hp Br 1-CaH7 305 1. 92 U. 38 T1Ia(Ol-C ll n-CaHo n-CiHn I n-CaHn 273 2. 54 0. 37 V0Cl(OnC I'I1)z CH; 1-C H C1 1-C(Hg 351 1.10 (J. 31! VOBrz(Oi- @2115 -CaHu Cl CzHa 270 0. 97 U. 41 V01 (On-C511") CH; n-CuHu C1 02115 283 l. 63 0. 40 VOClz(01-C$Hn) CH CeHi Cl CuHi 251 1. 27 0. 36 TiCla(On-CgH 3) CH; 1-CmH7 C1 p-CH CnH4 298 2. 73 0. TiCla(0 cyclo CrHn) CH Cyclo CuHu 01 Cyclo CaHu 264 1.82 0.38 T1Cl3(0 CflHfi) I1-C3H7 I1'C3H7 C1 Cyclo C5H9 208 2. 26 U. 29 TiC13(O-p-CHaC6H4) CzHr C2H5 C1 Cyclo 04H; 241 2.01 0.39

What is claimed is:

1. A process for producing an ethylene polymer which comprises polymerizing ethylene in the presence of a catalyst prepared by the reaction between (A) at least one compound of the general formula;

wherein R and R represent independently members selected from the group consisting of alkyl groups having one to five carbon atoms, cyclohexyl, phenyl and l-naphthyl; X and X represent members selected from the group consisting of alkyls having one to five carbon atoms, cycloalkyls having four to six carbon atoms, phenyl, p-tolyl and halogens selected from the group consisting of Cl, Br and I and at least one of X and X represents said halogen, and (B) at least one compound selected from the group consisting of l. TiX VX TiX (OR VO'X ,(OR and VOX wherein X represents halogen selected from the group consisting of Cl, Br, and l; R represents one member selected from the group consisting of alkyls having one to six carbon atoms, cyclohexyl, phenyl and p-tolyl; p is an integer of 2 to 4,1; is an integer of l to 3; r is an integer of 1 to 2; and

2. the solid compounds obtained by the reaction be- 4. A process according to claim 1, wherein the solid compound obtained by the reaction between one member selected from the group consisting of TiX.,, VX TiX (OR") VOX ,(OR and VOX and one member selected from the group consisting of AlR,,. (OR),,.X- SiR l-l, (RHSiO),,, R R"R SiO-(R HSiO) -Sir R"R' and a combination of one member selected from SiR H, (R"HS:O), and R'RRSiO--(R"1-lSiO),-RRR and one member selected from AlCl AlBr and FeCl;, is selected from the group consisting of the solid compounds obtained by the reaction between one member selected from the group consisting of TiCl TiCl (O nC H VCl and VOCl and one member selected from the group consisting of Al(C H Al(C 1-1 AlCl (C H Al(O C H )(C H Al(i-C H A1Cl(i- 4 s)z, a)a z s) a) ]4, (CH SiO- [(Cl-l )HSiO] Si(Cl-l and a combination of one member selected from the group consisting (Cl-l SiH, (C H SiH, [(CHQHSiO], and (Cl-l SiO [(CH )HSiO] Si(CI-l and one member selected from the group consisting of AlCl AlBr: and FeCl 5. A process according to claim 1, wherein the polymerization is conducted in the presence of at most 50 mole percent, based upon the ethylene reactant, of hydrogen.

6. A process for producing an ethylene copolymer containing at most 10 weight percent of one alphaolefin having three to 10 carbon atoms which comprises copolymerizing ethylene and said alpha-olefin in the presence of a catalyst prepared by the reaction between (A) at least one compound of the general formula;

wherein R and R represent independently members selected from the group consisting of alkyl groups having one to five carbon atoms, cyclohexyl, phenyl and l-naphthyl; X and X represent members selected from the group consisting of alkyls having 1 to 5 carbon atoms, cycloalkyls having four to six carbon atoms, phenyl; p-tolyl and halogens selected from the group consisting of Cl, Br and I and at least one of X and X represents said halogen, and (B) at least one compound selected from the group consisting of 1. rix VX TiX (OR VOX ,(OR and VOX wherein X represents halogen selected from the group consisting of Cl, Br, and I; R represents one member selected from the group consisting of alkyls having one to six carbon atoms, cyclohexyl, phenyl and p-tolyl; p is an integer of 2 to 4, q is an integer of l to 3; r is an integer of l to 2; and 2. the solid compounds obtained by the reaction between one member selected from the group consisting of TiX VX TiX ,,(OR VOX ,(OR and VOX and one member selected from the group consisting of AlR,,(OR X- SiR 1-l, (RHSiO),, R"R"RSiO-(R l-lSiO),-SiRRR and combination of one member selected from SiR H, (RHSiO), and RR*RSiO-(R HSiO),-SiRR R and one member selected from AlCl AlBr and FeCl wherein R and X represent independently the same groups as defined above; R and R represents independently the same groups abovedefined R R, R, R R, R and R 11 represent independently the same groups as above-defined R or R q and r represent independently the same integers as above-defined; v is an integer of l to 3, w is 0 or an integer of l to 2, y is an integer of 1 to 3andv+w+y=3;sisanintegerof3 to 6;tis at least one and the viscosity of RR"RSiO-(R"HSiO),--SiR'R"R is at most 2,000 centistrokes, the mole ratio of the compound (A) to the compound (B) being 0.5 5:1. 7. A process according to claim 6, wherein said alpha-olefin is one member selected from the group consisting of propylene, butene-l 3-methyl-butenel pentene-l, 4-methylpentene-l, hexene-l, heptene-l, oc-

tene-l, nonene-l and decene-l.

2% umfnsu 5'1 A'1 1ss lA'ljENl OFFICE CER TIFICATE OF CORRECTION Patent N0. 3, 787,323 Dated January 22I 122 ma ITSUHOAISHIMA ET'AL, (page 1 of 2' It is certified that error appears 1x1 the aboye-ide'ncified patent V and the: said Letters Patent are hereby corrected as shown below:

C01. 2, line 53, chapge. "(i-C H Hsi0A1Br to Co].. Z, line 55,- chan ge ."cycle" to cycle G01. 8, Table if: the fi ea dir xg, c a'nc el "new Belbw "Example" "andj 'ijnsert Yield below "Polymer". I C01. 8, '1ab1 e"I I, line 68 cancel "No." abeve 910". 7 e51. 10 line 2, claiin 2 aft;er 'groups"'insert as defined 'vi w 5 9 5 2 change 2 ?5& j 2% to C01. 10, 11ne'66 claim 2, change "(C to 0051. 1 1; betfieen' lines 13 end 1h, claim 3, in ss erit:

f UNITED :s'm'usa -1'A l bl% 1' ur 1' 1w. CER TIFICATE'OF CORRECTION Patent No. v Datd I Inven tofls) 4 i I (P g 9 It is ce rtified that error nppearsin-the aboye-ic i entiiied patent and that laid LetunPatent-arp hareby corrected as shown below:

I C015 1.1:, 1ine 39, ciaim h, chahge' "(R HS:0) i;o*- (3 11510) --.1

signe dl pdgseale d this. 7th day o fJanuary1975.

' (SEAL) I Attes t McCoy M; :GIBSQN JR. Attes'ting Officer v ,c. MARSHALL DANNQI Cpnunissioner of Patents 

1. TIX3P, VX3P, TIX34-Q(OR3)Q, VOX33-R(OR3)R AND VOX33 WHEREIN X3 REPRESENTS HALOGEN SELECTED FROM THE GROUP CONSISTING OF CL, BR, AND I; R3 REPRESENTS ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYS HAVING ONE TO SIX CARBON ATOMS, CYCLOHEXYL, PHENYL AND P-TOYL; P IS AN INTEGER OF 2 TO 4, Q IS AN INTEGR OF 1 TO 3; R IS AN INTEGER OF 1 TO 2; AND
 2. THE SOLID COMPOUNDS OBTAINED BY THE REACTION BETWEEN ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF TIX34, VX34, TIX34-Q(OR3)Q, VOX33-RAND VOX33 AND ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF AIR4R(OR5)UX33-Y, SIR63H, (R7HSIO)G, R8R9R10SIO-(R11SIO)T-SIR10R9R8 AND A COMBINATION OF ONE MEMBER SELECTED FROM SIRR63H, (R7HSO)G AND R8R9R10SIO-(R11HSIO)T-SIR10R9R8 AND ONE MEMBER SELECTED FROM ALCL3, ALBR3AND FECL3 WHEREIN R3 AND X3 REPRESENT INDEPENDENTLY THE SAME GROUPS AS DEFINED ABOVE; R4 AND R5 REPRESENTS INDEPENDENTLY THE SAME GROUPS ABOVEDEFINED R3; R6, R7, R8, R9, R10 AND R11 REPRESENT INDEPENDENTLY THE SAME GROUPS AS ABOVE-DEFINED R1 OR R2; Q AND R REPRESENT INDEPENDENTLY THE SAME INTEGERS AS ABOVE-DEFINED; V IS AN INTEGER OF 1 TO 3, W IS 0 OR AN INTEGER OF 1 TO 2, Y IS AN TEGER OF 1 TO 3 AND V+N+Y=3; S IS AN INTEGER OF 3 TO 6+ T IS AT LEAST ONE AND THE VISOSITY OF R8R9R10SIO-(R11HSIO)TSIR10R9B8 IS AT MOST 2,000 CENTISTROKES, THE MOLE RATIO OF THE COMPOUND (A) TO THE COMPOUND (B) BEING 0.5 - 5 :
 1. 